Method of forming a conductor pattern on the inside of a hollow tube by reacting a gas or fluid therein with actinic radiation

ABSTRACT

A technique for fabricating a patterned conductor on the inner surface of a transparent tube comprises providing a source of conductive material inside a hollow tube and directing actinic radiation onto the tube wall where the deposition of a conductive pattern is desired to deposit conductive material thereon. That conductive deposit may be thickened by subsequent electroless or electroplating. The result is an improved magnetic resonance sensor comprising a hollow tube having &#34;flat&#34; conductor coils disposed on its interior surface.

This application is a division of application Ser. No. 07/290,950, filedDec. 28, 1988, now U.S. Pat. No. 5,084,311, issued Jan. 28, 1992.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to electromagnetic transducers includingconductors disposed in predetermined patterns and more particularly topatterned conductors disposed on surfaces having significant curvatures.

2. Prior Art

For accurate transduction of electromagnetic signals, transducers musthave accurately known characteristics. Accurately known characteristicscan be obtained in two different ways. The first is to fabricateindividual transducers in an attempt to match a predeterminedconfiguration, but with a fabrication tolerance which requires extensivetesting to determine the actual characteristics of each transducer andwhether it meets the intended specifications. The second is to fabricatethe transducers with tight enough tolerances that simple testing can beused to establish that each transducer matches or fails to match thespecifications for a standard transducer of the same design whosecharacteristics are accurately known from extensive testing. In theformer case, substantial testing cost is added to the fabrication costof each transducer thereby substantially increasing its cost. In thelatter case the cost of extensive testing of the standard transducer ispart of the initial development cost which is spread over all productiontransducers. It is generally recognized that the latter technique ispreferable for both interchangeability of parts between systems and forlimiting manufacturing and testing costs. Unfortunately, not allelectromagnetic transducers are susceptible to fabrication to the tighttolerances necessary to enable the latter technique to be utilized. Onetype of transducer which has not been susceptible to being fabricated inthe latter way is the pickup coil of the sensors used in magneticresonance spectroscopy.

In magnetic resonance spectroscopy a strong uniform DC magnetic biasfield is applied to a sample to be analyzed. This magnetic field causesthe net spin axis of the electrons of the atoms comprising the sample toalign parallel to the DC magnetic bias field. The sensor or pick-up coilhas two halves and is located within this strong uniform magnetic fieldwith the sample being investigated disposed between the two halves. Aperturbation current is passed through this sensor coil to create amagnetic field perpendicular to the DC magnetic bias field to cause theorbits of electrons in the sample material to realign with their spin nolonger in the direction of the DC magnetic bias field, and preferablyperpendicular to the DC magnetic bias field. The perturbation current isthen removed from the sensor coil, which removes the perturbationmagnetic field. The spins of the electrons then reorient back toparallel to the DC magnetic bias field. The electromagnetic signalsgenerated by this reorientation of the electron spins are sensed by thepick-up coil and amplified and analyzed by the electronic portion of themagnetic resonance spectroscopy machine. The frequencies of theelectromagnetic signals are determined by the elements and compoundspresent in the sample and thus provide information which can beprocessed to determine the composition of the sample.

For maximum accuracy in the spectrographic analysis of the material ofthe sample, the sensor coil must have an accurately known configurationand must be configured in a way which causes the perturbation currentthrough the sensor coil to generate a magnetic field which is orientedperpendicular to the main DC magnetic bias field without any significantfield component parallel to the main DC bias field. Further, the pickupcoil itself should have no net turns through the bias magnetic field inorder that the current through the coil will not alter that DC magneticbias field.

One prior art magnetic resonance spectroscopy pick up coil is a hollowglass tube about 3/8 inch in inner diameter with a wall thickness ofabout 1/16 inch and having a sensor coil disposed on its outer surface.The sensor coil comprises two diametrically opposed "flat" or pancakecoils which conform to the exterior surface of the tube and areconnected in series. The sample to be analyzed is passed through thistube and analyzed when it is located in the tube between the two halvesof the sensor coil.

The sensor coil is formed through use of photolithographic techniques todefine the coil in a separate, planar, copper foil which is preferablyfree of all magnetic materials. The copper foil is etched to leave thecoil which is then mounted on and adhered to the exterior surface of theglass tube. Mounting the coil on the tube is a labor intensive processwhich is subject to significant variation even with the exercise ofgreat care by the operator. As a result, sensor coils of this type mustbe extensively and carefully quality control tested prior to beingaccepted for shipment, sale and use as a sensor coils. Both the manualfabrication process and the extensive testing it makes necessarycontribute significantly to the cost of such sensor coils. Since thebasic material costs are minimal, the fabrication process and testingare the primary contributors to the cost.

Improved and less expensive coil designs and fabrication techniques aredesirable.

Accordingly, it is an object of the present invention to provide amethod of fabricating a magnetic resonance sensor which is accuratelyreproducible whereby the need for extensive testing is obviated.

It is also an object of the invention is to provide a magnetic resonancesensor fabrication technique which is inexpensive in order that the costof such sensors may be reduced.

An additional object of the invention is to provide a technique forfabricating precision conductor patterns on surfaces having significantcurvature.

Another object of the invention is to provide a technique forfabricating precision patterned conductors on the surfaces of acylindrical object.

Another object of the invention is to provide a technique forfabricating precision patterned conductors on the interior surface of ahollow tube, which may be transparent.

A further object of the invention is to provide an improved magneticresonance sensor.

A still further object of the invention is to provide a magneticresonance sensor having improved sensitivity and accuracy.

A still further object of the invention is to provide a magneticresonance sensor in which the pick up coils are immediately adjacent tothe sample volume being investigated.

SUMMARY OF THE INVENTION

In accordance with the present invention, the above objects areaccomplished through photoreactive control of the patterning of aconductor on a surface having significant curvature. In accordance withone embodiment of this technique, a patterned conductor is provided onthe interior surface of a hollow tubular member which is transparent toa photoreactive wavelength of light. The reactive light is focussedthrough the wall of the tubular member onto the interior surface of thatwall in order to induce or catalyze the deposition of conductivematerial on those portions of the inner surface onto which the light isfocussed while a source material for the conductive material beingdeposited is present in the vicinity of that focussed light. The patternof the conductor is determined by relative movement between the focussedlight and the tube. A thicker conductive layer may be obtained bysubsequently depositing additional conductive material on top of thephotoreactively deposited material. Other patterning techniques may alsobe used.

An improved magnetic resonance sensor is provided in the form of ahollow tubular member which confines the sample during evaluation andhas the magnetic resonance sensor coils disposed on its interiorsurface. These coils may have more turns than prior art coils, whichincreases their sensitivity.

BRIEF DESCRIPTION OF THE DRAWINGS

The features of the invention believed to be novel are set forth withparticularity in the appended claims. The invention itself, however,both as to organization and method of operation, together with furtherobjects and advantages thereof, may best be understood by reference tothe following description taken in conjunction with the accompanyingdrawing(s) in which:

FIG. 1 illustrates, in perspective view, a prior art magnetic resonancesensor;

FIG. 2 illustrates, in plan view, a prior art sensor coil prior to itsapplication to the tube;

FIG. 3 illustrates, in partially cut away, perspective view, a magneticresonance sensor in accordance with the present invention;

FIG. 4 illustrates, in perspective view, an alternative pattern for aconductor disposed on the interior surface of a hollow tubular member;

FIG. 5 illustrates in partially perspective, partially block diagramform, an apparatus for fabricating transducers in accordance with thepresent invention; and

FIG. 6 illustrates a process of fabricating transducers in accordancewith the present invention.

DETAILED DESCRIPTION OF THE INVENTION

A state of the prior art magnetic resonance sensor for use inspectroscopy is illustrated in FIG. 1. The sensor 10 comprises a hollowglass tube 12 having an exterior surface 14 and an interior surface 16.For magnetic resonance spectroscopy, this tube is typically less than aninch in diameter and may have an inner diameter of about 3/8 inch. Aconductor pattern 20 is disposed on exterior surface 14 of the tube 12.The pattern 20 comprises two "flat" coils 22 which are connected inseries and have external leads 24 and 26 connected to opposing ends ofthe conductor. In accordance with the prior art fabrication techniques,the conductor pattern is initially formed by photolithographicprocessing of a copper foil to provide the conductor 20 in its flat coilform as shown in FIG. 2. Bridge connectors 28 are included in the etchedpattern of the foil in order to hold the coil pieces in their desiredrelative positions during assembly. The coils 22 are assembled on thetube 12 in diametrically opposed positions to form the sensor 10 ofFIG. 1. One assembly process involves applying a layer of epoxy to theexterior surface of the tube where the coil is to be located, laying thecoil in place and allowing the epoxy to cure. Thereafter, the coppertabs or bridges 28, shown in FIG. 2, are cut and removed to leave thedesired coil shape on the glass tube as shown in FIG. 1. This process islabor intensive, requires pains-taking skilled manipulation of smallparts, and results in sensor-to-sensor variations as a result ofcoil-to-coil variations in shape and placement. Substantial testing isrequired to insure that a given sensor 10 meets specifications beforethat sensor can be accepted for use. The sample to be analyzed bymagnetic resonance spectroscopy is passed through the tube 12 and eitherheld stationary or moved at a known rate during analysis. The sample isanalyzed when it is located between the two halves of the pickup coil.

A magnetic resonance sensor 100 in accordance with the present inventionis illustrated in FIG. 3. The sensor 100 comprises a glass tube 112having an outer surface 114 and an inner surface 116. A conductivepattern 120 is disposed on the inner surface 116 of tube 112. Thepattern 120 consists of two coils 122 connected in series, each of whichcomprises a plurality of oblong turns whose long sides run parallel tothe axis of the tube, and which are situated diametrically opposite eachother. The conductor 120 has first and second external leads 124 and126. The leads 124 and 126 preferably are attached to the exteriorsurface 114 of the tube and extend through holes 118 in the tube wallinto the interior of the tube. The holes 118 may be laser-drilled orfabricated in other ways. The connection from the winding 122 on theinside surface 116 to the external leads 124 and 126 may be viathrough-plating on the holes 118, via eyelets inserted in the holes, orby other appropriate means.

In accordance with the methods of fabrication to be describedhereinafter, the sensor 100 is accurately reproducible with the resultthat minimal testing is required to ensure that a given sensor 100 meetsspecifications. In particular, the problems of misorientation andvariations in the shape of and spacings between adjacent turns of thewinding are eliminated by the method of fabrication, with the resultthat once an acceptable configuration for the sensor 100 and itsconductive pattern 120 has been determined and produced, concerns aboutsensor-to-sensor variations in coil position, spacing and orientationare eliminated. As a result, simple testing is sufficient to certifythat the sensor meets specifications.

While the conductive pattern 120 is described and shown as beingdisposed on the inner surface 116 of the tube 112, it will be understoodthat although that is preferred, the patterned conductor may be disposedon the exterior surface 114 if desired. Such exterior placementincreases the spacing between the sample and the coil, which reducessensitivity and is therefore considered less desirable than interiorplacement. However, external placement is feasible where the differencein sensitivity is considered acceptable. Exterior placement of this coilstill provides substantial improvement over prior art sensors 10 becauseof the increased number of turns which may be provided in the inventivecoil and because of the increased precision with which the inventivecoil is fabricated. This precision minimizes the quantity of testingnecessary to certify that the sensor meets specifications and alsosubstantially eliminates the problem of rejection of finished sensors asnot meeting specifications, thereby increasing yield and reducing costs.

The method of this invention may be utilized to produce many differentconductor patterns on the surface of a tube or other structure having asignificant curvature to its surface. One such alternative pattern isshown in FIG. 4 where a transducer 200 comprise a tube 212 having anexterior surface 214 and an interior surface 216. A patterned conductor220 is disposed on the interior surface 216 of the tube 212. Theconductor 220 is in the form of a single helical spiral 222 having afirst external lead 224 connected to one end and a second external lead226 connected to its other end. Leads 224 and 226 are preferablyconnected to conductor 220 via through holes in the tubing wall. Thetransducer 200 is suitable for producing or responding to magneticfields which run axially of the tube 212.

Many variations on the conductor pattern are possible. These include,but are not limited to, a plurality of parallel conductors, which may behelical, for example, or a plurality of conductors connected in commonat one or both ends, and so forth. In accordance with the invention,almost any conductive pattern can be created, so long as it does notinvolve crossovers in which the second conductor to be defined would beshadowed by the first conductor deposited. The problem of shadowing canbe overcome by projecting the laser light through the tube wall on whichshadowing does not occur and through the gas within the tube to focus onthe tube wall on which shadowing does occur. Naturally, if crossingconductors are to be insulated from each other and are disposed on thesame wall surface, an insulating layer must be applied before the secondconductor is deposited.

The sensor 100 is preferably fabricated by the method illustrated inFIG. 6 using the apparatus shown schematically in FIG. 5.

The first step in the process is providing in the tube 112 a materialwhich will deposit a conductor on the wall of the tube where thephotochemically active or actinic light is focused. For example,tungsten hexafluoride (WF₆) mixed with hydrogen gas at a pressure ofabout 100 Torr has been used as this material in order to deposittungsten on the tube wall, but many other materials may be used. Theends of the tube are preferably closed with plugs to contain the desiredgas and to exclude undesirable gases. The terms photoreactive light,reactive light, photochemically active light and actinic light are usedinterchangeably in this specification and are used herein in the broadsense of producing a physical effect or change in or of material whichis exposed to it. This may involve a chemical change, evaporation,sublimation, delamination or any other physical change in accordancewith the circumstances.

The second step is mounting the tube 112 in a deposition system 70 whichincludes manipulation or drive apparatus 72 which is capable of rotatingthe tube about its longitudinal axis 113 and translating the tubeparallel to its longitudinal axis.

The third step is positioning and focusing a laser 74 which ispreferably a continuous wave (CW) laser to direct its emissions on thetube 112. A focusing objective 76 is adjusted to focus the laser's beamon the interior surface of the tube which is closest to the lasersource. A shutter 78 may be used to interrupt the laser beam. The entiresystem operates under the control of a control unit 80, or may bemanually operated. A laser having an emission spectrum which isphotochemically active is selected in accordance with the depositionprocess being used. Focusing of the laser may be accomplished before thetube is positioned or while the laser is directed at a portion of thetube 112 which is spaced from the desired location of the conductivepattern or it may be done while the laser is directed at a portion ofthe area where the conductive pattern is to be disposed.

Fourth, the laser is turned on and drive 72 rotates and translates tube112 in a pattern to cause the focused laser beam to trace, on theinterior surface 116 of the tube, the desired pattern of the conductivelayer 120 which, in the example given, comprises tungsten. The laserlight may be interrupted by shutter 78 or by turning off the laser powerat those times when it is desired to skip from one point to anotherwithout depositing a conductive trace. With an argon laser Model 2025-05made by Spectra Physics, operating at a power level of 50 mW, atranslation rate of up to 1 mm per second has been found to produce acontinuous conductive trace with the specified gaseous source material.Other source material pressures and other source materials may enable orrequire different tracing rates. The minimum conductive trace width isdetermined by the focus of the laser. Thus, in this example, when thelaser was focused to a spot of about 30 microns in diameter, a traceabout 20 microns wide resulted. Defocusing the laser to a spot size ofabout 100 microns resulted in a conductive trace having a width of about60 microns.

Fifth, for any of the conductive patterns where a high conductivity isdesired for the pattern, additional conductive material may be depositedon the initial laser-induced deposit, such as by electroless plating orelectroplating, to make the initial deposit thicker, more conductive andcapable of carrying larger currents. Such plating can also provide asubstantial reduction in the resistance of the winding. This isparticularly true where the initially deposited conductive material hasa relatively high resistance as compared to the subsequently depositedmaterial which may be a material such as electroplated copper which hasa substantially higher conductivity than tungsten.

Sixth, the external leads are attached to the ends of the coil.Alternatively, the external leads may be attached before laserdeposition or before the thickening deposition.

The source material in the foregoing process may be a liquid or a solidinstead of a gas at the time of exposure. For example, a solution ofpalladium acetate in chloroform was prepared and the interior of thetube coated with that solution by immersing the tube in the solution.The coating was air dried and then exposed to actinic radiation, asdiscussed above, to deposit palladium in the desired conductor pattern.The unexposed palladium acetate and the residues from the exposedpalladium acetate were then removed by rinsing the tube in chloroform.Copper was then deposited on the palladium using an electroless copperdeposition process in which the palladium catalyzed the deposition ofthe copper.

This same process can be performed using the palladium acetate inchloroform solution as a liquid source of the palladium by filling thetube with that solution and then illuminating the tube in the desiredpattern as heretofore described. In filling the tube with a liquidsource, pressure relief should be provided to ensure that any subsequentheating of the liquid by the laser beam will not result in an explosionor other damage to the tube, apparatus or operator.

Useful source materials include, but are not limited to carbonyl, alkyl,halide and hydrogen compounds of elements such as tungsten, zinc,aluminum, molybdenum, platinum, palladium, copper, gold and silicon. Anycompound containing a metallic element whose deposition can be inducedby light may be used as a source material.

Many alternative methods may be used to produce coils in accordance withthe present invention. For example, a continuous conductive film may bedeposited on the interior surface of the tube and the laser then focusedthrough the tube wall onto the interface between the conductive layerand the glass with sufficient power applied to cause the conductivelayer to sublime, evaporate or otherwise evolve or separate from thesurface in a pattern which leaves the conductor only in those locationswhich correspond to a predetermined pattern.

In another alternative embodiment, a solvent-based acrylated liquid coatof photoresist, such as Fanton™ photoresists available from ArmstrongWorld Industries, Inc., may be deposited on the interior surface of thetube, exposed by laser tracing through the tube wall and then developedto leave the photoresist on the interior surface of the tube in thenegative of the desired conductor pattern. This tracing may be executedusing the same apparatus (shown in FIG. 5) as that used for the directdeposition of conductive material from a gas as has been described.Fanton photoresist is presently preferred for this use because itsexposure is much less sensitive to its thickness than other photoresistsare. The conductor may then be deposited over the photoresist and thephotoresist removed to lift off the conductor except where the conductoris directly disposed on the tube surface.

As a further alternative, a continuous conductive film may be formed onthe interior surface of the tube and the Fanton photoresist depositedover the conductive film. The photoresist is then exposed using laserlight directed onto the photoresist from the interior of the tube. Whilea variety of means may be used for directing this laser light, opticalfibers are suitably small in diameter and capable of carrying sufficientlight intensity to expose the photoresist in accordance with a tracingof the spot on the surface. Thereafter the photoresist is developed, thedeposited conductor is etched or otherwise removed where the photoresisthas been removed, and then the remaining or protective portion of thephotoresist is removed to leave the desired conductor pattern on theinterior of the tube surface. This conductor pattern may also bethickened by electroless or electroplating or other deposition asdesired.

While the discussion thus far has been in terms of conductor patternsdisposed on the interior surface of the glass tube, similar conductorpatterns may be provided on the exterior surface of the tube with thesame precision and repeatability benefits as have been described for theinterior placement of the conductor pattern.

While only certain preferred features of the invention have beenillustrated and described herein, many modifications and changes willoccur to those skilled in the art. It is, therefore, to be understoodthat the appended claims are intended to cover all such modificationsand changes as fall within the true spirit of the invention.

What is claimed is:
 1. A method of forming a desired conductor patternon the inner surface of a hollow tubular member comprising:providingsaid hollow tubular member; providing within said hollow tubular membera source of a conductive material to be deposited on said inner surfaceof said tubular member; providing a source of photochemically activelight having a wavelength which is capable of causing said conductivematerial to deposit from said source material onto said inner surface ofsaid tubular member; and directing said light onto said inner surface ina pattern corresponding to said desired conductor pattern to causedeposition of said conductive material from said source material onto anextended longitudinal portion of said inner surface, where either saidhollow tubular member is transparent to said light or said light isdirected onto said inner surface via an optical fiber inserted withinthe interior of said hollow tubular member where said light strikes saidinner surface.
 2. The method recited in claim 1 wherein:the step ofproviding a source material comprises providing a fluid source material.3. The method recited in claim 2 wherein said fluid source materialcomprises a compound of a metallic element.
 4. The method recited inclaim 3 wherein said metallic element is selected from the groupconsisting of tungsten, zinc, aluminum, molybdenum, platinum, palladium,copper, gold and silicon.
 5. The method recited in claim 2 furthercomprising, after the directing step:increasing the thickness of thepatterned conductor by depositing additional conductive material on saidpatterned conductor.
 6. The method recited in claim 1 wherein:the stepof providing a source material comprises providing a gaseous sourcematerial.
 7. A method of forming a patterned conductor on the innersurface of a hollow tubular member comprising:providing said hollowtubular member; forming a continuous layer of conductive material on atleast an extended longitudinal portion of the inner surface of saidhollow tubular member; and selectively removing portions of saidcontinuous layer of conductive material from said extended longitudinalportion of the inner surface of said tubular member in accordance with apattern of light impinging on said layer to leave a predeterminedpattern of conductive material on the extended longitudinal portion ofthe inner surface of said tubular member, where either said hollowtubular member is transparent to said light or said light is directedonto said inner surface via an optical fiber inserted within theinterior of said hollow tubular member.
 8. The method recited in claim 7wherein the removing step comprises:providing a source of light; anddirecting the light from said source on the portions of said continuouslayer of conductive material which it is desired to remove in anintensity and for a time sufficient to cause the conductive materialilluminated thereby to separate from said inner surface of said tubularmember and from the portions of said conductive layer which were notexposed to said light.
 9. The method recited in claim 8 wherein saidtubular member is transparent to said light and said light is directedthrough the thickness of the wall of said tubular member onto thesurface of the conductive layer which is in contact with said wall. 10.The method recited in claim 9 wherein said light is directed onto saidconductive layer from within the hollow interior of said hollow tubularmember.
 11. The method recited in claim 9 wherein the directing stepcomprises passing said light through an optical transmission systemwhich extends into the hollow interior of said tubular member.
 12. Themethod recited in claim 11 wherein the step of passing said lightthrough an optical transmission system comprises passing said lightthrough a fiber optic transmission system.
 13. The method recited inclaim 8 wherein the step of providing a source of light comprisesproviding a laser having a wavelength suitable for performing theselectively removing step.
 14. The method recited in claim 13 whereinthe step of depositing said photoresist layer comprises depositing alayer of solvent-based acrylated liquid photoresist.
 15. The methodrecited in claim 7 wherein the light from said source is directed ontosaid layer in the form of a small spot and wherein said method furthercomprises moving said spot relative to said tubular member in a patternwhich traces the area from which conductive material is to be removed.16. The method recited in claim 7 wherein the selectively removing stepcomprises:depositing a layer of photoresist over said conductive layerin the interior of said hollow tubular member; exposing and developingsaid photoresist in a pattern corresponding to said desired conductorpattern; and removing the portions of said conductive layer which arenot protected by said photoresist.
 17. The method recited in claim 16further comprising, after the step of removing the unprotectedconductive material:removing the remaining portions of said photoresistlayer from the remaining portions of said conductive layer.
 18. Themethod recited in claim 17 further comprising after the step of removingsaid remaining portions of said photoresist layer:increasing thethickness of said conductive pattern by depositing additional conductivematerial onto the remaining portions of said conductive layer.